Back to EveryPatent.com
| United States Patent |
5,204,383
|
|
Manabe
, et al.
|
April 20, 1993
|
Dental adhesives
Abstract
According to the present invention, a dental adhesive comprising glyceryl
mono(meth)acrylate and a polymerizable monomer having at least one
olefinic double bond and capable of copolymerizing with said glyceryl
mono(meth)acrylate is provided.
| Inventors:
|
Manabe; Atsufumi (Tokyo, JP);
Itoh; Kazuo (Tokyo, JP);
Wakumoto; Sadao (Tokyo, JP);
Hasegawa; Tokuji (Yokohama, JP);
Koike; Toshie (Kawasaki, JP)
|
| Assignee:
|
Kuraray Co., Ltd. (Kurashiki, JP);
Mitsui Petrochemical Industries, Ltd. (Tokyo, JP)
|
| Appl. No.:
|
892725 |
| Filed:
|
May 29, 1992 |
Foreign Application Priority Data
| Mar 28, 1990[JP] | 2-81768 |
| Mar 28, 1990[JP] | 2-81769 |
| Current U.S. Class: |
523/118; 433/226; 525/466; 526/273; 526/278; 526/317.1; 526/320; 526/329.4 |
| Intern'l Class: |
A61K 006/02; A61K 006/08 |
| Field of Search: |
523/118,116
525/466
433/226
526/273
|
References Cited
U.S. Patent Documents
| 4645456 | Feb., 1987 | James | 433/217.
|
Primary Examiner: Schofer; Joseph L.
Assistant Examiner: Zitomer; Fred
Attorney, Agent or Firm: Sherman and Shalloway
Parent Case Text
This application is a continuation of application Ser. No. 07/590,814,
filed Oct. 1, 1990.
Claims
What is claimed is:
1. A dental adhesive comprising glyceryl mono(meth)acrylate and a
polymerizable monomer having at least one olefinic double bond and capable
of copolymerizing with said glyceryl mono(meth)acrylate,
wherein the polymerizable monomer is a polymerizable acid monomer having at
least one olefinic double bond and at least one acid group selected from
the group consisting of
##STR27##
in which Z represents halogen, and further the above-mentioned groups do
not link to hydroxyl, halogen or
##STR28##
and said
##STR29##
group links to an organic group having at least 8 carbon atoms.
2. The dental adhesive as claimed in claim 1 wherein said adhesive is in
the form of said mixture of glyceryl mono(meth)acrylate and said
polymerizable monomer having at least one olefinic double bond and capable
of copolymerizing with said glyceryl mono(meth)acrylate.
3. A dental adhesive as claimed in claim 1 wherein said adhesive is in the
form of at least two packs, one containing said glyceryl
mono(meth)acrylate, and at least one other containing said polymerizable
monomer having at least one olefinic double bond and capable of
copolymerizing with said glyceryl mono(meth)acrylate.
4. The dental adhesive as claimed in claim 2 or 3 wherein said glyceryl
mono(meth)acrylate is dissolved in a volatile organic solvent having a
boiling point of below 200 .degree. C. at atmospheric pressure, water or a
mixture thereof.
Description
FIELD OF THE INVENTION
This invention relates to dental adhesives having excellent properties of
bonding a tooth and a dental restorative material together, and having
excellent properties of marginal sealing between the tooth and material
thus bonded.
BACKGROUND OF THE INVENTION
In the field of dental goods and materials, there have recently been
developed various adhesives having excellent adhesiveness to a tooth,
especially to a dentinal portion thereof. Used as adhesive components in
such adhesives as referred to above are polymerizable monomers having acid
groups in the molecule. These polymerizable monomers which are known, per
se, include (meth)acrylate monomers such as those having in the molecule
phosphoric acid diester groups (Japanese Patent L-O-P Publn. No.
113089/1977), phosphoric acid monoester groups (Japanese Patent L-O-P
Publn. No. 21607/1983), carboxyl group or acid anhydride groups (Japanese
Patent L-O-P Publn. No. 11149/1979) and acid halide groups (Japanese
Patent L-O-P Publn. No. 151607/1982).
However, even in the adhesives containing such adhesive monomers as
mentioned above, a further improvement is desired in that when a dental
restorative material (filling material, metal, etc.) is applied to a
tooth, a further improved adhesion between the tooth and material is
obtained and, moreover, no gap is formed in the marginal gap between the
tooth and material thus united.
OBJECT OF THE INVENTION
The present invention has been made in view of the prior art as mentioned
above, and an object of the invention is to provide dental adhesives which
are excellent in adhesive properties and, in addition thereto, excellent
in marginal sealing properties capable of inhibiting the formation of
marginal gap between a tooth and a dental restorative material applied
thereto.
SUMMARY OF THE INVENTION
The dental adhesives of the present invention are characterized by
comprising glyceryl mono(meth)acrylate and a polymerizable monomer having
at least one olefinic double bond and capable of copolymerizing with said
glyceryl mono(meth)acrylate.
The dental adhesives of the invention as illustrated above may be in the
form of a mixture containing glyceryl mono(meth)acrylate and a
polymerizable monomer having at least one olefinic double bond and capable
of copolymerizing with said glyceryl mono(meth)acrylate.
The dental adhesives of the invention mentioned above may also be in the
form of at least two packs, one containing glyceryl mono(meth)acrylate,
and at least the other containing a polymerizable monomer having at least
one olefinic double bond and capable of copolymerizing with said glyceryl
mono(meth)acrylate.
DETAILED DESCRIPTION OF THE INVENTION
The dental adhesives of the present invention comprise glyceryl
mono(meth)acrylate and a polymerizable monomer copolymerizable with said
glyceryl mono(meth)acrylate.
Glyceryl mono(meth)acrylate has two hydroxy groups in the molecule, and
therefore the dental adhesives comprising glyceryl mono(meth)acrylate and
a polymerizable monomer copolymerizable with said glyceryl
mono(meth)acrylate have excellent adhesive properties and excellent
marginal sealing properties capable of inhibiting the formation of
marginal gap between a tooth and a dental restorative material.
Gyceryl mono(meth)acrylate include as isomers 1,3-dihydroxyisopropyl
(meth)acrylate and 2,3-dihydroxypropyl (meth)acrylate, and
2,3-dihydroxypropyl (meth)acrylate is preferred in point of adhesive
properties. Usually, methacrylate monomers are used more frequently than
acrylate monomers.
The polymerizable monomer used in the invention includes (meth)acrylic acid
esters, (meth)acrylamides, maleic acid esters, fumaric acid esters, vinyl
esters such as vinyl acetate, styrene and derivatives thereof, and vinyl
compounds such as acrylonitrile and acrolein. Of these monomers as
exemplified above, particularly preferred are (meth)acrylic acid esters.
Exemplified as (meth)acrylic acid esters are methyl (meth)acrylate,
2-hydroxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate,
triethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate,
2,2-bis 4-(3-methacryloyloxy-2-hydroxy-propoxy)phenyl propane (Bis-GMA),
trimethylolethane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate
and N,N-dimethylaminoethyl methacrylate.
Further, as the polymerizable monomers preferably used in the invention,
there may be mentioned polymerizable acid monomers having at least one
acid group selected from the group comprising
##STR1##
(in which Z represents halogen, and further the above-mentioned groups do
not link to hydroxyl, halogen or
##STR2##
and at least one olefinic double bond.
As the polymerizable acid monomers as illustrated above, there may be used
such compounds as will be exemplified below.
(i) The compounds having the group
##STR3##
include those represented by the following formulas.
##STR4##
(ii) The compounds having the group
##STR5##
include those represented by the following formulas.
##STR6##
(iii) The compounds having the group
##STR7##
include those represented by the following formulas.
##STR8##
(iv) The compounds having the groups
##STR9##
include those represented by the following formulas.
##STR10##
(v) The compounds having the group
##STR11##
include those represented by the following formulas.
##STR12##
(vi) The compounds having the group
##STR13##
include that represented by the following formula.
##STR14##
(vii) The compounds having the group
##STR15##
include those represented by the following formulas.
##STR16##
(viii) The compounds having the group
##STR17##
include that represented by the following formula.
##STR18##
(IX) The compounds having the group
##STR19##
include those represented by the following formulas.
##STR20##
As mentioned above, the dental adhesives of the present invention comprise
glyceryl mono(meth)acrylate and a polymerizable monomer, preferably a
polymerizable acid monomer capable of copolymerizing with said glyceryl
mono(meth)acrylate, and are used usually in the following form.
(1) The dental adhesive used is in the form of a system comprising a
mixture of glyceryl mono(meth)acrylate and a polymerizable monomer,
preferably a polymerizable acid monomer capable of copolymerizing with
said glyceryl mono(meth)acrylate, or of the above-mentioned system to
which a third component such as a solvent, filler or polymerization
initiator has been added if necessary.
In the dental adhesives used in the above-mentioned form, the amount, based
on the total weight of the adhesive, of glyceryl mono(meth)acrylate
contained is 0.01-50% by weight, preferably 0.1-30% by weight, and
similarly that of the polymerizable acid monomer contained is 0.01-50% by
weight, preferably 0.1-30% by weight.
Because of a one-packtype formulation, the dental adhesives mentioned in
the foregoing (1) are easy in handling in comparison with the dental
adhesives as will be formulated in the undermentioned (2) and have no
practical difficulties in respect to their storage stability.
The dental adhesives having the formulation of such mixture as mentioned
above are used by applying them on a tooth, especially a dentin.
(2) The dental adhesive used is in the form of a system comprising a
package containing a composition [A] in which glyceryl mono(meth)acrylate
has been contained and a package containing a composition [B] in which a
polymerizable monomer, preferably a polymerizable acid monomer capable of
copolymerizing with said glyceryl mono(meth)acrylate has been added.
The dental adhesives having such a formulation as mentioned above are used
in such a manner that the composition [A] is first applied on a tooth,
especially a dentin, and the composition [B] is laminated by applied on
the surface of the composition [A] thus coated.
The composition [A] contains glyceryl mono(meth)acrylate and a volatile
organic solvent having a boiling point of below 200 .degree. C. at
atmospheric pressure or water or mixtures thereof and if necessary,
copolymerizable monomers, polymerization initiators, fillers, etc. The
amount, based on the total weight of the composition [A], of glyceryl
mono(meth)acrylate contained therein is 0.1-80% by weight, preferably
1-50% by weight, and similarly that of the polymerizable acid monomer
contained is 0.01-50% by weight, preferably 0.1-30% by weight.
The composition [B] usually contains a polymerization initiator in addition
to the above-mentioned polymerizable monomer, and if necessary, may
contain a solvent, fillers, etc. Furthermore, the composition [B] may be
formulated into a two-divided pack system.
The content in the composition [B] of the above-mentioned polymerizable
monomer is 0.01-50% by weight, preferably 0.1-30% by weight. The weight
proportion of the composition [A] to the composition [B] used in the
dental adhesives is from 1:100 to 10:1, preferably from 1:10 to 2:1.
The solvent preferably used in the dental adhesives of the present
invention includes volatile organic solvents having boiling point below
200 .degree. C. at atmospheric pressure, for example, alcohols such as
methanol, ethanol, allyl alcohol, isopropanol and 1-octanol; ketones such
as acetone, methyl ethyl ketone and phorone; ethers such as ethyl ether,
1,4-dioxane, diethylene glycol and diethyl ether; esters such as ethyl
acetate, butyl acetate and 2-ethylhexyl acetate; and hydrocarbons such as
hexane, undecane, toluene, xylene, methylene chloride, 1,2-dichloroethane
and 1,1,2,2-tetrachloroethane, or water or mixtures thereof.
The polymerization initiator used in the dental adhesives of the dental
adhesives of the invention includes benzoyl peroxide-aromatic tertiary
amine systems, peroxides such as cumene hydroperoxide, tributyl borane,
and aromatic sulfinic acid (or salts thereof) -aromatic secondary or
tertiary amine-acylperoxide systems, and further includes
photopolymerization initiators such as .alpha.-diketone (e.g.
camphorquinone, diacetyl or benzyl) -reducing agent systems and benzoin
methyl ether, etc.
The filler used in the adhesives of the invention includes inorganic
fillers such as glass, quartz, hydroxyapatite, calcium carbonate, barium
sulfate, aluminum oxide, titanium oxide and zirconium oxide, and polymer
powders such as polymethyl methacrylate, polystyrene and polyvinyl
chloride, etc.
The dental adhesives of the invention are used in the same manner as in the
case of common dental adhesive. Namely the present dental adhesives are
applied on a tooth, and then the dental restorative material such as a
filling material, metal or the like is applied to the surface of the thus
coated tooth.
EFFECT OF THE INVENTION
The dental adhesives of the present invention have excellent adhesive
properties to a tooth, especially dentin and, at the same time, are
excellent in properties of marginal sealing between the tooth and the
dental restorative material applied thereto Accordingly, the present
dental adhesives are useful for various dental purposes wherein such
effects as mentioned above are required, especially for restoring teeth
suffering from caries including particularly cervical dentin.
The present invention is illustrated below in detail with reference to
examples, but it should be construed that the invention is in no way
limited to those examples.
EXAMPLE 1
A composition (A) comprising 35 parts by weight of 2,3-dihydroxypropyl
methacrylate (glyceryl mono(meth)acrylate and 65 parts by weight of water
was applied to the flat surface of dentin of an extracted human tooth
abraded with #1000 abrasive paper and treated with 0.5M aqueous EDTA
solution, followed by air blowing. The flat surface of dentin thus applied
was further coated with a commercially available dental adhesive [Clearfil
New Bond containing 10-methacryloyloxydecryl dihydrogenphosphate (a
polymerizable acid monomer), a product of Kuraray Co., Ltd.] followed by
air blowing, and then placed with a commercially available composite resin
(Clearfil F II, a product of Kuraray Co., Ltd. containing Bis-GMA,
triethyleneglycol dimethacrylate and quartz filler) followed by air
blowing. The thus treated tooth was immersed in water at 37 .degree. C.
for 24 hours and then subjected to tensile bond strength test to obtain a
tensile bond strength of 153 kg/cm.sup.2.
EXAMPLE 2
In each of 10 extracted human molar teeth, an adamantine adjacent to a
dentin was removed, the dentin thus exposed was then flatted with #1000
abrasive paper, and a cylindrical cavity of 3 mm in diameter and 1.5 mm in
depth was formed on the flatted dentin. The cavity thus formed was then
treated inside with 0.5M aqueous EDTA solution for 60 seconds, followed by
water washing and then drying. Thereafter, the composition (A) used in
Example 1 was applied to the whole inner wall of the cavity, followed by
air blowing. The inner wall of the cavity was coated with Clearfil New
Bond followed by air blowing, and the cavity was filled with Clearfil F
II, followed by setting.
Immediately thereafter, the tooth thus treated was immersed in water at
room temperature, and allowed to stand for 10 minutes. Thereafter, the
filled portion of the cavity was mirror polished to expose the cavity
verge, and an interfacial border between the cavity verge and the filling
materials was observed by means of a optical microscope (NIKON,
OPTIPHOTO.times.400) so as to ascertain whether a gap is formed or not. As
the result, no gap was observed at all over the whole circumferential
verge of all of 10 specimens, and a good bonded state was shown in every
case.
EXAMPLE 3
Example 2 was repeated except that the cavity was filled with a
commercially available composite resin (PhotoClearfil A, a product of
Kuraray Co., Ltd. containing Bis-GMA, triethyleneglycol dimethylacrylate,
quartz filler and photoinitiator) in place of Clearfil F II, and the
composite resin was cured by irradiation with light for 40 seconds by
means of a visible light irradiation equipment (QuickLight manufactured by
Kuraray Co., Ltd.), followed by the same test as in Example 2. The results
obtained were good, showing that the specimens in which no gap was
observed at all in the whole marginal gap of the cavity were 9 cases out
of 10.
EXAMPLE 4
Example 2 was repeated except that a composition comprising 35 parts by
weight of 2,3-dihydroxypropyl methacrylate, 35 parts by weight of water
and 30 parts by weight of ethanol was used in place of the composition
(A), followed by the same test as in Example 2. The results obtained were
good, showing that the specimens in which no gap was observed were 9 cases
out of 10.
EXAMPLE 5
The flat surface of a dentine of extracted human tooth abraded with #1000
abrasive paper was treated with 0.5M aqueous EDTA solution for 60 seconds,
followed by water washing and then drying. The flat surface thus treated
was applied with the undermentioned composition (B), followed by
irradiation with light for 20 seconds by means of a visible light
irradiation equipment (Quicklight manufactured by Kuraray Co., Ltd.).
Thereafter, the flat surface thus treated was placed with a commercially
available photocuring composite resin (PhotoClearfil, a product of Kuraray
Co., Ltd. containing Bis-GMA, triethyleneglycol dimethylacrylate, quartz
filler and photoinitiator), and cured by irradiation with light from
QuickLight for 40 seconds. The thus treated tooth was immersed in water at
37.degree. C. for 24 hours, and was then subjected to tensile bond
strength test to obtain a tensile bond strength of 141 kg/cm.sup.2.
______________________________________
Composition (B)
______________________________________
2,3-Dihydroxypropyl methacrylate
30 parts by weight
Bis-GMA 60 parts by weight
10-Methacryloyloxydecyl
10 parts by weight
dihydrogen phosphate
Camphor quinone 0.5 parts by weight
Ethyl N,N-dimethyl-p-aminobenzoate
0.5 parts by weight
______________________________________
EXAMPLE 6
In each of 10 extracted human molar teeth, an adamantine adjacent to a
dentine was removed, the dentine thus exposed was then flattened with
#1000 abrasive paper, and a cylinder cavity of 3 mm in diameter and 1.5 mm
in depth was formed on the flattened dentine. The cavity thus formed was
then treated inside with 0.5M aqueous EDTA solution for 60 seconds,
followed by water washing and then drying. Thereafter, the composition (B)
was applied to the whole inner wall of the cavity, followed by air blowing
and then irradiating with light for 20 seconds by means of a visible light
irradiation equipment (Quicklight manufactured by Kuraray Co., Ltd.). The
cavity was filled with a commercially available composite resin
(Photoclearfill A, a product of Kuraray Co., Ltd.), and cured by
irradiation with light for 40 seconds, followed by setting.
Immediately thereafter, the tooth thus treated was immersed in water at
room temperature, and allowed to stand for 10 minutes. thereafter, the
filled portion of the cavity was mirror polished to expose the cavity
verge, and an interfacial border between the cavity verge and the filler
was observed by means of a light microscope (NIKON, OPTIPHOTO.times.400)
so as to ascertain whether a clearance is formed or not.
The results obtained were the same as those obtained in Example 3.
EXAMPLES 7-12
In each of 10 extracted human molar teeth, an adamantine adjacent to a
dentine was removed, the dentine thus exposed was then flattened with
#1000 abrasive paper, and a cylindrical cavity of 3 mm in diameter and 1.5
mm in depth was formed on the flattened dentine. The cavity thus formed
was then treated inside with 0.5M aqueous EDTA solution for 60 seconds,
followed by water washing and then drying. Thereafter, the undermentioned
composition (C) was applied to the whole inner wall of the cavity,
followed by air blowing and then irradiating with light for 20 seconds by
means of visible light irradiation equipment (Quicklight manufactured by
Kuraray Co., Ltd.). The cavity was filled with a commercially available
composite resin (Photoclearfill A, a product of Kuraray Co., Ltd.), and
cured by irradiation with light for 40 seconds, followed by setting.
Immediately thereafter, the tooth thus treated was immersed in water at
room temperature, and allowed to stand for 10 minutes. thereafter, the
filled portion of the cavity was mirror polished to expose the cavity
verge, and an interfacial border between the cavity verge and the filler
was observed by means of a light microscope (NIKON, OPTIPHOTO.times.400)
so as to ascertain whether a clearance is formed or not.
The results obtained were good as shown in Table 1.
______________________________________
Composition (C)
______________________________________
Triethylene glycol dimethacrylate
30 parts by weight
Bis-GMA 50 parts by weight
Polymerizable acid monomer
20 parts by weight
(as disclosed in Table 1)
Camphor quinone 0.5 parts by weight
Ethyl N,N-dimethyl-p-
0.5 parts by weight
aminobenzoate
______________________________________
TABLE 1
__________________________________________________________________________
Number of
specimens having
Example
Polymerizable acid monomer no gap
__________________________________________________________________________
7
##STR21## 10
8
##STR22## 9
9
##STR23## 9
10
##STR24## 10
11
##STR25## 9
12
##STR26## 10
__________________________________________________________________________
COMPARATIVE EXAMPLE 1
Example 1 was repeated except that only Bond was applied to the tooth
without using the composition (A), followed by the same adhesion test as
in Example 1. The tensile bond strength as measured was 102 kg/cm.sup.2.
COMPARATIVE EXAMPLE 2
Example 2 was repeated except that only Clearfil New Bond was applied to
the cavity without using the composition (A), followed by the same test as
in Example 2. As the result, the specimens in which no gap was observed at
all in the whole marginal gap were 6 cases out of 10.
COMPARATIVE EXAMPLE 3
Example 2 was repeated except that a composition comprising 35 parts by
weight of 2-hydroxyethyl methacrylate and 65 parts by weight of water was
applied to the cavity in place of the composition (A), followed by the
same test as in Example 2. As the result, the specimens in which no gap
was observed at all were 7 cases out of 10.
COMPARATIVE EXAMPLE 4
Example 5 was repeated except that the composition (B) containing propyl
methacrylate in place of the 2,3-dihydroxypropyl methacrylate was used,
followed by the same adhesion test as in Example 5. The tensile bond
strength as measured was 75 kg/cm.sup.2.
COMPARATIVE EXAMPLE 5
Example 6 was repeated except that the composition (B) containing propyl
methacrylate in place of the 2,3-dihydroxypropyl methacrylate was used,
followed by the same test as in Example 6. As the result, the specimens in
which no gap was observed in the whole marginal gap were 4 cases out of
10.
Top